Polyepoxy compounds having an amide linkage

ABSTRACT

The present invention provides compounds that have an amide linkage and at least two epoxy groups. The compounds are preferably aliphatic.

FIELD OF INVENTION

The present invention relates to compounds containing at least two epoxygroups and at least one amide linkage. The invention further relates tocompositions containing these compounds and to network polymers obtainedby curing the compositions.

BACKGROUND OF THE INVENTION

Epoxy compounds are widely used, for instance in heat and/or radiationcurable compositions. Despite the widespread use of conventional epoxycompounds, there is still an ongoing demand to provide epoxy compoundswith improved characteristics.

SUMMARY

The present invention provides:

Compounds containing

-   -   (i) at least one amide linkage, preferably at least two amide        linkages; and    -   (ii) at least two epoxy groups, preferably at least two terminal        epoxy groups.        Compounds containing at least one amide linkage and at least two        epoxy groups are hereinafter also referred to as polyepoxy        amides. Preferred polyepoxy amides include those represented by        the following formulae (1) to (6):        wherein:    -   n represents an integer of at least 2;    -   x represents an integer of at least 1, preferably at least 2;    -   y, z, m, p, and q represent integers of at least 1;    -   R³, R⁵, R⁶, and R⁷ independently represent a homo- or        hetero-hydrocarbylene or -hydrocarbylidene group, preferably a        homo-alkylene group; and    -   R¹, R², and R⁴ independently represent hydrogen or a homo- or        hetero-hydrocarbyl group, preferably hydrogen or a homo-alkyl        group.

The present invention further provides compositions, and networkpolymers obtained by curing these compositions, wherein the compositionscontain at least one polyepoxy amide. It is preferred that compositionsaccording to the present invention further contain a curing agent.

Polyepoxy amides represented by any one of the following formulae (9),(11), or (12):

Compositions containing at least one polyepoxy amide.

Compositions containing at least one polyepoxy amide, a curing agent;and, optionally, a further reactive component; and compositionscontaining at least one polyepoxy amide, a curing agent, and,optionally, a polymerization catalyst(s).

Such compositions further containing at least one additive(s), or atleast one solvent(s), or both.

Materials for coatings, for composites, and/or for other applications,that are or contain said composition(s).

Network polymers formed from the compositions.

Materials containing the network polymers. Coatings, composites, resincastings, films, adhesives and other materials containing the networkpolymers.

DETAILED DESCRIPTION OF THE INVENTION

Definitions

A homoalkyl group refers to an alkyl group consisting essentially ofcarbon and hydrogen atoms. A heteroalkyl group refers to an alkyl groupwhich further contains other atoms, which may be present either in themain chain or, preferably, as substituents. Such other atoms include,for instance, oxygen, nitrogen, sulfur, and halogen atoms. Preferably atleast 40 weight percent (wt %) of the heteroalkyl group is comprised ofcarbon and hydrogen atoms, more preferably at least 60 Wt %, even morepreferably at least 80 wt %, and most preferably at least 90 wt %. Boththe homoalkyl and heteroalkyl groups may include cyclic structures.Preferred substituents for homoalkyl groups include methyl, ethyl, andpropyl groups. Preferred substituents for heteroalkyl groups furtherinclude hydroxyl, nitro, cyano, and halogen groups.

A homo-hydrocarbyl group refers to a hydrocarbon group that is amonovalent radical; homo-hydrocarbylene and homo-hydrocarbylidene groupsrefer to hydrocarbon groups that are divalent radicals. These groups mayinclude cyclic structures and/or unsaturated bonds, and thus may includearomatic structures (for example, aryl groups, arylene groups).Hetero-hydrocarbyl, hetero-hydrocarbylene, and hetero-hydrocarbylidenegroups refer, respectively, to homo-hydrocarbyl, homo-hydrocarbylene,homo-hydrocarbylidene groups which further contain other atoms which maybe present either in the main chain or, preferably, as substituents.Such other atoms include, for instance, oxygen, nitrogen, sulfur, andhalogen atoms. Preferably at least 40 wt % of the hetero-hydrocarbongroup is comprised of carbon and hydrogen atoms, more preferably atleast 60 wt %, even more preferably at least 80 wt %, and mostpreferably at least 90 wt %. Preferably the homo- and hetero-hydrocarbongroups are saturated. Preferred substituents for homo-hydrocarbon groupsinclude methyl, ethyl, and propyl groups. Preferred substituents forhetero-hydrocarbon groups further include hydroxyl, nitro, cyano, andhalogen groups.

In a preferred embodiment, a hydrocarbon group or radical will containless than 100 main chain atoms, more preferably less then 80, even morepreferably less than 50, still more preferably less than 30, yet morepreferably less than 25, and even still more preferably less than 20main chain atoms. A hydrocarbon group or radical will contain at least 1main chain atom. In a preferred embodiment, a hydrocarbon group orradical will contain at least 2 main chain atoms, more preferably atleast 3, even more preferably at least 4, still more preferably at least5, yet more preferably at least 6, and even still more preferably atleast 7 main chain atoms. In a preferred embodiment, a hydrocarbon groupor radical will contain 5 main chain atoms; in a preferred embodiment, ahydrocarbon group or radical will contain 8 main chain atoms; in apreferred embodiment, a hydrocarbon group or radical will contain 11main chain atoms; in a preferred embodiment, a hydrocarbon group orradical will contain 14 main chain atoms. In a particularly preferredembodiment, a hydrocarbon group or radical will contain 8 main chainatoms. In a preferred embodiment, all main chain atoms will be carbonatoms. Hydrocarbon groups and radicals include, for example, alkyl,alkylidene, alkenyl, alkenylene, aryl, arylene, alkylaryl, aliphatic,and cycloaliphatic groups and radicals.

Polyepoxy Amides

A polyepoxy amide according to the present invention, is a compoundcontaining:

-   -   (i) at least one amide linkage, preferably at least two amide        linkages; and    -   (ii) at least two epoxy groups, preferably at least two terminal        epoxy groups.        Compounds containing at least one amide linkage and at least two        epoxy groups are hereinafter also referred to as polyepoxy        amides. Preferred polyepoxy amides include those represented by        the following formulae (1) to (6):        wherein:    -   n represents an integer of at least 2;    -   x represents an integer of at least 1, preferably at least 2;    -   y, z, m, p, and q represent integers of at least 1;    -   R³, R⁵, R⁶, and R⁷ independently represent a homo- or        hetero-hydrocarbylene or -hydrocarbylidene group, preferably a        homo-alkylene group; and    -   R¹, R², and R⁴ independently represent hydrogen or a homo- or        hetero-hydrocarbyl group, preferably hydrogen or a homo-alkyl        group.

The epoxy compounds having at least one amide linkage may be formed by:(1) providing at least one carboxylic acid containing at least oneunsaturation, preferably a terminal unsaturation (anomega-unsaturation); (2) providing at least one amino-organic compoundthat is a monoamino-, diamino-, triamino-, or polyamino-organiccompound, preferably an at least diamino-organic compound; (3) reactingsaid amino compound(s) with the carboxylic acid(s) to form at least oneamide containing both at least one amide linkage and at least twounsaturations; and (4) then epoxidating at least two unsaturationspresent in the amide to form an epoxy compound having at least one amidelinkage. However, where a monoamino-organic compound is used, themonoamino-organic compound will itself contain at least one unsaturationthat can be epoxidated under the reaction conditions used to epoxidatean unsaturation present in the portion(s) of the amide that wascontributed by the carboxylic acid(s). Amidation and epoxidationreactions are well known in the art and are useful, respectively, forthe purposes of forming and then epoxidating the amides hereof.

In a preferred embodiment, the carboxylic acid containing at least oneunsaturation will contain at least 3 main chain atoms, more preferablyat least 4, even more preferably at least 5, still more preferably atleast 6, yet more preferably at least 7, and even still more preferablyat least 8 main chain atoms. In a preferred embodiment, the carboxylicacid containing at least one unsaturation will contain less than 100main chain atoms, more preferably less then 80, even more preferablyless than 50, still more preferably less than 30, yet more preferablyless than 25, and even still more preferably less than 20 main chainatoms. Preferably, the carboxylic acid containing at least oneunsaturation will contain 4, 5, 6, 8, 10, 11, 12, 14, 16, 17, 18, 20,22, 24, 26, 28, or 30 main chain atoms; more preferably 8, 10, 11, 12,14, 16, 17, or 18 main chain atoms. Even more preferably, the carboxylicacid containing at least one unsaturation will contain 8, 11, 14, or 17main chain atoms. In a particularly preferred embodiment, the carboxylicacid containing at least one unsaturation will contain 11 main chainatoms. In a preferred embodiment, all main chain atoms will be carbonatoms. In a preferred embodiment, the carboxylic acid will be amono-carboxylic acid. In a preferred embodiment, the carboxylic will bea mono-unsaturated carboxylic acid.

In preferred embodiment, the carboxylic acid will be at least one ofpropenoic, 3-butenoic, 4-pentenoic, 5-hexenoic, 6-heptenoic, 7-octenoic,8-nonenoic, 9-decenoic, 10-undecenoic, 11-dodecenoic, 12-tridecenoic,13-tetradecenoic, 14-pentadecenoic, 15-hexadecenoic, 16-heptadecenoic,17-octadecenoic, 18-nonadecenoic, 20-heneicosenoic, 22-tricosenoic,24-pentacosenoic, or 26-heptacosenoic acid. More preferably, thecarboxylic acid will be at least one of 5-hexenoic, 6-heptenoic,7-octenoic, 10-undecenoic, 12-tridecenoic, 14-pentadecenoic,16-heptadecenoic, 18-nonadecenoic, 20-heneicosenoic, or 22-tricosenoicacid. Even more preferably, the carboxylic acid will be at least one of10-undecenoic, 12-tridecenoic, 14-pentadecenoic, or 16-heptadecenoicacid. In a particularly preferred embodiment, the carboxylic acid willbe 10-undecenoic acid. The carboxylic acid containing at least oneunsaturation will preferably be, or be derived from, abiologically-produced unsaturated fatty acid, for example, oleic acid.The carboxylic acid containing at least one unsaturation can be derivedfrom a biologically-produced unsaturated fatty acid by, for example, ametathesis reaction such as is commonly known in the art. Carboxylicacids containing at least one unsaturation are widely commerciallyavailable.

In a preferred embodiment, the amino-organic compound will be an aminethat is an aryl amine, alkylaryl amine, aliphatic amine, orcycloaliphatic amine. In a preferred embodiment, the amine will be adiamine, triamine, or higher amine. In a preferred embodiment, the aminewill contain at least one primary amino group; more preferably at leasttwo primary amino groups. In a preferred embodiment, the amine willcontain at least one secondary amino group. The amine may contain bothprimary amino group(s) and secondary amino group(s). Where the aminecontains more than one secondary amino group, preferably the secondaryamino groups will be separated from each other approximatelyequidistantly along the main chain of the amine. In a preferredembodiment, the amine will contain at least 2 amino groups. In apreferred embodiment, the amine will contain up to about 10 aminogroups; more preferably up to about 8, even more preferably up to 6, andstill more preferably up to 5 amino groups. In a preferred embodiment,the amine will contain 3 amino groups. In a preferred embodiment, theamine will contain 2 amino groups. In a preferred embodiment, the aminewill contain at least 3 main chain atoms, more preferably at least 4main chain atoms. In a preferred embodiment, the amine will contain upto about 30 main chain atoms, more preferably up to about 20 main chainatoms, even more preferably up to about 15 main chain atoms, and stillmore preferably up to about 10 main chain atoms.

Illustrative examples of preferred diamines include, but are not limitedto: ethylene diamine; 1,2-diaminopropane; 1,3-diaminopropane;N,N′-dialkyl-1,3-propanediamine; 1,4-butanediamine; 1,6-hexanediamine,and phenylene-diamine. Illustrative examples of preferred triaminesinclude, but are not limited to: diethylene-triamine;ethylene-trimethylene-triamine; bis(trimethylene)triamine; and melamine.Illustrative examples of preferred higher amines include, but are notlimited to: triethylene-tetramine; tris(trimethylene)tetramine;tetraethylene-pentamine; and pentaethylene-hexamine. Particularlypreferred amines include ethylene diamine, 1,3-diaminopropane,diethylene-triamine, and triethylene-tetramine. Amines may be preparedby any of the many methods well known in the art; amines are widelycommercially available.

The reacting of the carboxylic acid with the amine to form the amide maybe accomplished by any of the methods known in the art. For example, thecarboxylic acid may, and preferably will, first be converted to an acidhalide, preferably an acid chloride. Among the methods known for thispurpose is treatment of the acid, or a carboxylate salt made therefrom,with, for example: sulfonyl chloride, oxalyl chloride, phosphorusoxychloride, phosphorus trichloride, phosphorus pentachloride, orphosgene (carbonyl chloride); or with a corresponding bromide; or withcyanuric fluoride. Carboxylic acid halides are also commerciallyavailable. The acid halide may then be contacted with the amine, in anorganic solvent, to form the amide. Preferably, the organic solvent is amoderately polar organic solvent, for example, tetrahydrofuran (THF),diethylether, chloroform, methylene chloride, pyridine, or dioxane.

Once formed, the amide may then be epoxidized by treatment with anactive oxygen agent, in an organic solvent, to epoxidize unsaturationspresent therein. For example, a peroxy-carboxylic acid [RC(O)OOH] orsalt thereof, such as peracetic acid, perpropionic acid, perbenzoicacid, bicarbonate-activated peroxide (percarbonate ion), sodium orpotassium percarbonate, or magnesium monoperoxyphthalate, may be used asthe active oxygen agent. Preferably, the organic solvent will be amoderately polar organic solvent, such as is described above. As aproduct of such an epoxidation reaction, an epoxy compound having atleast one amide linkage is obtained.

The polyepoxy amides may be used in, or used to form, compositions. Thecompositions containing the polyepoxy amide(s) may be used to formnetwork polymers obtained by curing these compositions. It is preferredthat compositions according to the present invention further contain acuring agent. The compositions may contain a polymerization catalyst(s),a further reactive component(s), an additive(s), or a solvent(s). Thecompositions may be used in various applications, for example: ascoatings, as materials for coatings, as matrix materials for composites,and other applications.

Curing Agent

Preferred curing agents include aliphatic amines, aromatic amines,isocyanates, polyfunctional hydroxyl containing compounds, anhydrides,polyfunctional acids, imidazoles, polyfunctional mercaptans, borontrihalide complexes, dicyanamides, and mixtures thereof.

Suitable aliphatic amine curing agents include, for instance,1,2-diaminocyclohexane, isophorone diamine, ethylenediamine,diethylenetriamine, triethylenetetraamine, tertraethylenepentamine,ethanolamine, piperazine, aminoethylpiperazine, aminoethylethanolamine,diethylaminopropylamine, dimethylaminopropylamine,2,5-dimethyl-2,5-hexanediamine, bis(aminocyclohexyl)methane,3-amino-1-cyclohexylaminopropane, polyethanolamine, polypropanolamine,polyethyleneimine, and mixtures thereof.

Suitable aromatic amine curing agents include, for instance,diaminobenzene, methylenedianiline, oxydianiline,diaminodiphenylsulfide, diaminodiphenylsulfone,2,4-bis-(p-aminobenzyl)aniline, diaminotoluene, ketimine, amidoamine,and mixtures thereof.

Suitable polyfunctional hydroxyl containing compounds include novolacs(thermoplastic phenol-formaldehyde resins obtained primarily by the useof acid catalysts and excess phenol), resoles (alkaline-catalyzed,thermosetting phenol-formaldehyde resins consisting primarily ofpartially condensed phenol alcohols), and bisphenols such as bisphenol A(4,4′-isopropylidenediphenol), bisphenol F [bis(4-hydroxyphenyl)methane]and 2,2′-bisphenol.

Suitable anhydrides include, for instance, benzophenone tetracarboxylicacid anhydride, chlorendic anhydride, succinic anhydride,dodecenylsuccinic anhydride, hexahydrophthalic anhydride, maleicanhydride, methyl hexahydrophthalic anhydride, tetrahydrophthalicanhydride, NADIC methyl anhydride(3a,4,7,7a-tetrahydromethyl-4,7-methanoisobenzofuran-1,3-dione),phthalic anhydride, polyadipic polyanhydride, polyazelaic polyanhydride,polysebasic polyanhydride, pyromellitic anhydride, and mixtures thereof.

Suitable polyfunctional acids include, for instance, adipic acid,sebasic acid, azelaic acid, terephthalic acid, isophthalic acid,cyclohexanedicarboxylic acid, and mixtures thereof.

Suitable imidazoles include, for instance, 2-methylimidazole,2-hydroxypropylimidazole, 2-heptadecylimidazole,1-benzyl-2-methylimidazole, 2-ethyl-4-methylimidazole,1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole,2-phenyl-4,5-dihydroxymethylimidazole, and mixtures thereof.

Suitable boron trihalide complexes include, for instance, borontrifluoride diethyl etherate.

Iodonium salts (for example, diaryliodonium salts), and sulfonium salts(for example, triarylsulfonium salts) may also be used as curing agents.A preferred diaryliodonium salt is diaryliodonium hexafluoroantimonate.The compositions containing iodonium salts and sulfonium salts may alsocontain any suitable photosensitizer such as, for instance, anthracene,pyrene, perylene, and mixtures thereof.

The compositions may also contain a suitable polymerization accelerator.Suitable polymerization accelerators include, for instance,multifunctional acrylate monomers, phenolics, monofunctional acids,novolacs, and bisphenols.

Suitable phenolics include, for instance, 4-tert-butylphenol, catechol,2-chlorophenol, 4-nitrophenol, 2,4-dimethylphenol and nonylphenol.

Suitable multifunctional acrylates include, for instance, tripropyleneglycol diacrylate and trimethylolpropane triacrylate.

Suitable monofunctional acids include, for instance, salicylic acid,5-chlorosalicylic acid, 2,4-dichlorobenzoic acid and valeric acid.

Suitable bisphenols include for instance, bisphenol A(4,4′-isopropylidenediphenol), bisphenol F [bis(4-hydroxyphenyl)methane]and 2,2′-bisphenol.

Polymerization Catalyst

The present compositions may contain a suitable polymerization catalyst.Examples of suitable polymerization catalysts include, for instance,tertiary amines, Lewis acids, onium salts, and imidazoles.

Suitable tertiary amines include, for instance, benzyldimethylamine,2-dimethylaminomethylphenol, and 2,4,6-tris(dimethylaminomethyl)phenol.

Suitable Lewis acids include, for instance, stannous octoate anddibutyltin dilaurate.

Suitable onium salts which can be used as a catalyst include, forinstance, ammonium salts (for example, tetrabutylammonium bromide).

Further Reactive Components

The present compositions may contain, besides one or more of thepolyepoxy amides, any further suitable reactive components such as, forinstance, other epoxy-functional components, hydroxy-functionalcomponents, acrylate-functional components, as well as mixtures thereof.For instance, the present compositions may contain the diglycidyl etherof bisphenol A. Preferred diglycidyl ethers of bisphenol A include thoserepresented by the following formula (7):

wherein n² represents an integer of 0 to 10.Additives

The compositions of the present invention may contain any suitableadditives. For instance, pigments may be added to color thecompositions. Other suitable additives which may be added include, forinstance, stabilizers (for example, antioxidants), rheology controlagents, flame retardants, light stabilizers, flow modifiers, colorstabilizers, inert fillers, and combinations thereof. Inert fillers canbe inorganic (for example, glass beads, talc, silica particles, orclays) or organic (for example, polysaccharides, modifiedpolysaccharides, and naturally occurring particulate fillers) or both.

Water and Organic Solvent

The compositions may contain water and/or organic solvents, for instanceto facilitate spraying the present compositions on a substrate.

Curing and Properties

Curing of the present compositions may be initiated by any suitablemeans, for instance by heat and/or radiation, such as ultraviolet (UV)radiation or electromagnetic radiation. Because the present polyepoxyamides contain at least two epoxy groups, the present compositions canform a crosslinked network upon cure, which crosslinked network is alsoreferred to as a “network polymer”.

Thermoplastic Polymers

The present polyepoxy amides may also be used to form thermoplasticpolymers. For instance, they may be polymerized with, e.g., dicarboxylicacids to form thermoplastic polyesters. An illustrative example of sucha polymerization is given below:

wherein:

A and Z independently represent hydrogen or a homo- orhetero-hydrocarbyl group, preferably hydrogen or a homo-alkyl group; and

-   -   B, X, Y, and Q independently represent a homo- or        hetero-hydrocarbylene or hetero-hydrocarbylidene group,        preferably a homo-alkylene group.        Applications

The polyepoxy amides may be used in a wide variety of applications. Forinstance, they can be used to obtain coatings, matrix materials forcomposites (for example, for composites that are reinforced with fiberssuch as glass fibers, polyamide fibers, polyester fibers, carbon fibers,or naturally occurring fibers such as wood, jute, ramie, flax, bamboo,or sisal fibers, or combinations thereof), adhesives, and molded parts.For instance, compositions containing the present polyepoxy amides maybe used to coat substrates, for instance wood, metal, or plasticsubstrates. The compositions may be applied as a solid or as a liquid.Preferably the compositions are applied as a liquid and by spraying thecompositions onto the substrate.

EXAMPLES

The following examples are given as particular embodiments of theinvention and to demonstrate the practice and advantages thereof. It isto be understood that the examples are given by way of illustration andare not intended to limit the specification or the claims that follow inany manner.

Synthesis of N,N′-ethylenebis(10-undecenamide)

To a 500 mL, three-necked round bottom flask (fitted with a refluxcondenser, addition funnel, and stir bar) was added 10-undecenoylchloride (32.2 mL, 30.4 g, 0.150 mol) and tetrahydrofuran (THF) (200mL). To the addition funnel was added ethylenediamine (4.51 g, 0.075mol), triethylamine (42 mL, 30.5 g, 0.300 mol), and THF (75 mL). Theamine solution was added dropwise to the acid chloride solution over onehour, yielding a white precipitate. On completion of addition, thereaction mixture was stirred at 25° C. for one hour. The reactionmixture was then filtered to remove precipitated solids. Theprecipitated solids were added to water (250 mL) and stirred. Theinsoluble solid was collected via filtration, then air dried. The crudeproduct was recrystallized from a mixture of acetone (500 mL) and water(20 mL) to produce a white solid which was dried in vacuo (that is,under vacuum) at 25° C. for 6 hours. The thus obtained compound isrepresented by formula (8) shown below. Yield: 10 g (34%). Melting point(M.P.): 146-148° C. ¹H and ¹³C NMR analyses were consistent with thestructure of formula (8).

Synthesis of epoxidized N,N′-ethylenebis(10-undecenamide)

To a 500 mL, three-necked round bottom flask (fitted with a refluxcondenser, addition funnel, and stir bar) was added undecenamideaccording to the above formula (8) (8.90 g, 22.7 mmol, 45.3 mmol doublebonds), sodium acetate (0.63 g), and methylene chloride (170 mL). To theaddition funnel was added 32 wt % peracetic acid (19.1 mL of 32 wt %,21.6 g of 32 wt %, 6.91 g of peracetic acid, and 90.9 mmol of peraceticacid). The peracetic acid solution was added dropwise over 20 minutes tothe suspension of formula (8) in methylene chloride, which had beencooled to 15° C. The reaction mixture was stirred at 25° C. for onehour, during which time the amide dissolved/reacted. The reactionmixture was then heated at reflux for 16 hours. The reaction mixture wasthen cooled to 15° C. in an ice bath, after which a solution of 60%(w/v) sodium bisulfite (9.44 g, 90.8 mmol) in water (200 mL) was addeddropwise to the reaction mixture. A white solid/gel precipitated fromsolution. The solid was collected via suction filtration. The aqueousand organic phases were discarded. The crude product was recrystallizedfrom a 2:1 mixture of acetone/ethanol (400 mL), then dried in vacuo at25° C. for 16 hours. The thus obtained polyepoxy amide is represented byformula (9) shown below. Yield: 5.93 g (61%). Epoxide equivalent weight(EEW): 218.8 g/mol epoxide (calculated EEW=212.3).

Synthesis of N,N′-(1,3-propylene)bis(10-undecenamide)

To a 500 mL, three-necked round bottom flask (fitted with a refluxcondenser, addition funnel, and stir bar) was added 10-undecenoylchloride (32.2 mL, 30.4 g, 0.150 mol) and THF (200 mL). To the additionfunnel was added 1,3-diaminopropane (5.56 g, 0.075 mol), triethylamine(42 mL, 30.5 g, 0.300 mol), and THF (75 mL). The amine solution wasadded dropwise to the acid chloride solution over one hour, yielding awhite precipitate. On completion of addition, the reaction mixture wasstirred at 25° C. for one hour. The reaction mixture was filtered toremove precipitated solids. The precipitated solids were added to water(250 mL) and stirred. The insoluble solid was collected via filtration,then air dried. The crude product was recrystallized from hot toluene(250 mL) to produce a white solid which was dried in vacuo at 25° C. for16 hours. The thus obtained compound is represented by formula (10)shown below. Yield: 9.6 g (31%). M.P.: 117° C. tol 19° C. ¹H and ¹³C NMRanalyses were consistent with the structure of formula (10).

Synthesis of epoxidized N,N′-(1,3-propylene)bis(10-undecenamide)

To a 100 mL, three-necked round bottom flask (fitted with a refluxcondenser, addition funnel, and stir bar) was added undecenamideaccording to the above formula (10) (4.07 g, 10.0 mmol, 20.0 mmol doublebonds) and methylene chloride (50 mL). To the addition funnel was addeda solution of sodium acetate (0.17 g) in 32 wt % peracetic acid (5.05 mLof 32 wt %, 5.71 g of 32 wt %, 1.83 g peracetic acid, and 24.0 mmolperacetic acid). The peracetic acid solution was added dropwise over 20minutes to the suspension of formula (10) in methylene chloride, whichhad been cooled to 15° C. The reaction mixture was stirred at 25° C. forone hour, during which time the amide dissolved/reacted. The reactionmixture was then heated at reflux for 15 hours. The reaction mixture wasthen cooled to 15° C. in an ice bath, after which a solution of sodiumsulfite (3.02 g, 24.0 mmol) in water (30 mL) was added dropwise to thereaction mixture. The organic and aqueous layers were then separated.The organic solution was washed consecutively with equal volumes ofwater, 5% (w/v) NaCl (twice), and 5% (w/v) NaHCO₃ (twice). The organiclayer was then dried over MgSO₄, filtered, and solvent was removed underreduced pressure to yield a white solid. The crude product wasrecrystallized from acetone (100 mL) to which water (1 mL) had beenadded. The recrystallized product was dried in vacuo at 25° C. for 4hours. The thus obtained polyepoxy amide is represented by formula (11)shown below. Yield: 1.65 g (38%). M.P. 119-122° C. Epoxide equivalentweight (EEW): 224.6 g/mol epoxide (calculated EEW=219.3).

Synthesis of diethylenetriamine-N,N′,N″-tri(10,11-epoxyundecamide)

Diethylenetriamine-N,N′,N″-tri(10,11-undecenamide), 20 g (0.031 moles),and 352.9 g of chloroform were charged to a 500 mL reaction vessel andcooled to 13° C. 26.3 g of 32 wt % peracetic acid (0.11 moles) in aceticacid (containing 0.78 g, 0.01 moles of sodium acetate) was added withstirring while maintaining the temperature below 15° C. After additionof the peracetic acid addition, the temperature was raised to 40° C. andmaintained for 7 hours before cooling to ambient temperature wherestirring was continued for an additional 16 hours. The reaction mixturewas again cooled to below 15° C. and the excess peracid was neutralizedby dropwise addition of 104.6 g of 10% (w/v) aqueous sodium sulfitewhile maintaining a temperature below 15° C. The organic and aqueousphases were allowed to separate and the organic phase was washedrepeatedly with water until a pH 6 was reached. The washed organic phasewas dried over anhydrous sodium sulfate overnight and then thechloroform was stripped off in vacuo to yield 20.5 g of crude product.The thus obtained polyepoxy amide is represented by formula (12) shownbelow. Recrystallization of the crude product from warm hexane yielded10.75 g, of diethylenetriamine-N,N′,N″-tri(10,11-epoxyundecamide) withan epoxide value of 18.8 wt % (94.7% of theory).

Preparation of a cured resin composition containingdiethylenetriamine-N,N′,N″-tri(10,11-epoxyundecamide)

1.5060 g of diethylenetriamine-N,N′,N″-tri(10,11-epoxyundecamide) and anequivalent amount of 4,4′-methylenedianiline (0.2996 g) were combinedand placed into a 120° C. oven for 7 minutes to dissolve the4,4′-methylenedianile. After the 4,4′methylenedianiline was dissolved,the resinous mixture was poured into a small aluminum pan. To the 1.3393g of the resinous mixture in the aluminum pan, 0.033 g of stannousoctoate was added. This mixture was then placed back into the oven whereit was cured according to the following schedule: 2 hours at 120° C.,2.5 hours at 140° C., and 2.5 hours at 180° C. Upon cooling to roomtemperature, a casting of the material was obtained from the aluminumpan. Differential scanning calorimetry analysis for this casting wasconducted at a heating rate of 1° C. per minute from 25° C. to 250° C.This analysis showed a glass transition temperature of 84° C.

The above description illustrates specific embodiments of the presentinvention; it will be understood that many modifications thereof willreadily be apparent to those skilled in the art, and it is intendedtherefore that this invention be limited only by the spirit and scope ofthe following claims.

1-11. (canceled)
 12. A network polymer formed by curing a compositioncontaining: (i) a polyepoxy amide represented by any one of thefollowing formulae (2), (3), (4), (5), or (6):

wherein: n represents an integer of at least 2; x represents an integerof at least 1; y, z, m, p, and q represent integers of at least 1; R²independently represents hydrogen or a homo- or hetero-hydrocarbylgroup; R³ independently represents a homo- or hetero-hydrocarbylenegroup that is an aliphatic group, and R³ independently contains 8 toless than 30 main chain atoms; R⁴ represents hydrogen; R⁵ independentlyrepresents a homo-hydrocarbylene or -hydrocarbylidene group; R⁶ and R⁷independently represent a homo- or hetero-hydrocarbylene or-hydrocarbylidene group; (ii) a curing agent; and (iii) optionally, afurther reactive component.
 13. The network polymer of claim 12, whereinsaid polyepoxy amide is represented by any one of formula (5) or formula(6).
 14. The network polymer of claim 12, wherein said polyepoxy amideis represented by any one of the following formulae (9), (11), or (12):


15. The network polymer of claim 12, wherein said further reactivecomponent is an epoxy resin that is not a polyepoxy amide.
 16. Thenetwork polymer of claim 12, wherein said further reactive component isa diglycidyl ether of bisphenol A.
 17. The network polymer of claim 12,wherein said composition further contains an additive that is anantioxidant, a flame retardant, a pigment, a flow modifier, a colorstabilizer, an inert filler, or a combination thereof.
 18. A resincasting, a film, an adhesive layer, or a bonding agent, containing thenetwork polymer of claim
 12. 19. (canceled)
 20. A coated substratecontaining the network polymer of claim
 12. 21. The coated substrate ofclaim 20, wherein the substrate includes metal, plastic or wood. 22.(canceled)
 23. A composite containing: (i) the network polymer of claim12; and (ii) a reinforcing agent.
 24. The composite of claim 23, whereinthe reinforcing agent includes fibers.
 25. The composite of claim 24,wherein the fibers are glass-, carbon-, polyamide-, or polyester-fibers.26. The composite of claim 24, wherein the fibers are wood, jute, ramie,flax, or sisal.
 27. The composite according to claim 23, wherein thereinforcing agent includes a non-fibrous filler.
 28. The composite ofclaim 27, wherein the non-fibrous filler is carbon, glass,polysaccharides, modified polysaccharides, or a naturally occurringparticulate matter.
 29. A thermoplastic polymer obtained by polymerizinga composition containing: (i) a polyepoxy amide represented by any oneof the following formulae (2), (3), (4), (5), or (6):

wherein: n represents an integer of at least 2; x represents an integerof at least 1; y, z, m, p, and q represent integers of at least 1; R²independently represents hydrogen or a homo- or hetero-hydrocarbylgroup; R³ independently represents a homo- or hetero-hydrocarbylenegroup that is an aliphatic group, and R³ independently contains 8 toless than 30 main chain atoms; R⁴ represents hydrogen; R⁵ independentlyrepresents a homo-hydrocarbylene or -hydrocarbylidene group; R⁶ and R⁷independently represent a homo- or hetero-hydrocarbylene or-hydrocarbylidene group; (ii) a curing agent; and (iii) optionally, afurther reactive component.
 30. The thermoplastic polymer of claim 29,wherein said polyepoxy amide is represented by any one of formula (5) orformula (6).
 31. The thermoplastic polymer of claim 29, wherein saidpolyepoxy amide is represented by any one of the following formulae (9),(11), or (12):


32. The thermoplastic polymer of claim 29, wherein the curing agent is apolyamine, polyacid, polyphenol, or anhydride.
 33. The thermoplasticpolymer of claim 32, wherein the polyepoxy amide contains only two epoxygroups and the polyamine curing agent contains only two reactivehydrogens, the polyacid curing agent is a dicarboxylic acid, and thepolyphenol curing agent is a diphenol.
 34. The thermoplastic polymer ofclaim 33, wherein the curing agent is a polyamine that contains only tworeactive hydrogens or is a dicarboxylic acid.
 35. The thermoplasticpolymer of claim 29, wherein said polymer is a polyester obtained bypolymerizing the polyepoxy amide with a dicarboxylic acid.
 36. Thenetwork polymer of claim 15, wherein said network polymer is formed bycuring a composition containing a polyepoxy amide represented by any oneof formulae (9), (11), or (12) of claim
 14. 37. The network polymer ofclaim 16, wherein said network polymer is formed by curing a compositioncontaining a polyepoxy amide represented by any one of formulae (9),(11), or (12) of claim
 14. 38. The network polymer of claim 17, whereinsaid network polymer is formed by curing a composition containing apolyepoxy amide represented by any one of formulae (9), (11), or (12) ofclaim
 14. 39. The resin casting, film, adhesive layer, or bonding agentof claim 18, wherein the network polymer thereof is formed by curing acomposition containing a polyepoxy amide represented by any one offormulae (9), (11), or (12) of claim
 14. 40. The coated substrate ofclaim 20, wherein the network polymer thereof is formed by curing acomposition containing a polyepoxy amide represented by any one offormulae (9), (11), or (12) of claim
 14. 41. The composite of claim 23,wherein the network polymer thereof is formed by curing a compositioncontaining a polyepoxy amide represented by any one of formulae (9),(11), or (12) of claim
 14. 42. The composite of claim 27, wherein thenetwork polymer thereof is formed by curing a composition containing apolyepoxy amide represented by any one of formulae (9), (11), or (12) ofclaim
 14. 43. The thermoplastic polymer of claim 32, wherein saidthermoplastic polymer is obtained by polymerizing a compositioncontaining a polyepoxy amide represented by any one of formulae (9),(11), or (12) of claim
 31. 44. The thermoplastic polymer of claim 35,wherein said polyepoxy amide is represented by any one of formulae (9),(11), or (12) of claim 31.